Esters of aminobenzoic acid

ABSTRACT

1. A COMPOUND OF THE FORMULA:   (H2N-),(Y-COO-X-OOC-)BENZENE   WHEREIN X REPRESENTS AN ALKYLENE RADICAL HAVING UP TO 4 CARBON ATOMS AND Y IS METHYL, ETHYL, ISOPROPYL, TRIFLUOROMETHYL, ACETYLETHYL, BENZYL, 2&#39;&#39;,4&#39;&#39;-DICHLOROPHENOXY-METHYL, 2&#39;&#39;,4&#39;&#39;-DICHLOROPHENOXYETHYL, VINYL, STYRYL, PHENYL, CHLOROPHENYL, TOLYL, OR METHOXYPHENYL.

United States Patent @ffice 3,839,411 ESTERS F AMINOBENZOIC ACID Jean Marie Louis Leroy, Rouen, and Claude Marie Henri Emile Brouard, Sotteville les Rouen, France, assignors to Ugine Kuhlmann, Paris, France N0 Drawing. Original application Oct. 4, 1968, Ser. No. 765,013, now Patent No. 3,663,530. Divided and this application Feb. 5, 1971, Ser. No. 113,096

Int. Cl. C07c 101/66 US. Cl. 260-471 R 3 Claims ABSTRACT OF THE DISCLOSURE Water-insoluble dyestuffs are provided having the in which E represents a p-phenylene or p-naphthylene radical linked to the nitrogen atoms, m represents the number 0 or 1, X represents an alkylene radical having up to 4 carbon atoms, Z and Z each represent a hydrogen or halogen atom or an alkyl, alkoxy, or acylamino group having up to 4 carbon atoms, Y represents an aliphatic, arylaliphatic, aromatic or heterocyclic radical, D represents the residue of a coupling compound of the benzene, diphenylene-oxide, indazole, coumarin, acetylacetarylide, pyrazolone or hydroxy-quinoline series, D represents the residue of a coupling compound of the benzene, diphenylene-oxide, indazole, coumarin, acetylacetarylide, hydroxy-quinoline, 1-pheny1-3-methyl-pyrazolone or 1-phenyl-3-carbonamidopyrazolone series, the nuclei A, B, D, and D and Y containing no solubilising acid groups.

These dyestuffs are useful for the colouration of hydrophobic textile materials and may be prepared from novel diazotisable bases of the general formula:

COOX-O--COY in which X and Y are as defined above.

The present application is a division of application Ser. No. 765,013, filed Oct. 4, 1968, now US. Pat. No. 3,663,530.

The present invention relates to new intermediate products and to new water-insoluble monoor disazo-dyestuffs, which are particularly interesting for the colouration of hydrophobic textile materials, especially textile materials based on aromatic polyesters.

These new dyestuffs may be represented by the general formulae:

3,839,411 Patented Oct. 1, 1974 in which B represents a paraphenylene or paranaphthylene radical linked to the nitrogen atoms, m represents the number 0 or 1, X represents an alkylene radical having up to 4 carbon atoms, Z and Z each represent a hydrogen or halogen atom or an alkyl, alkoxy, or acylamino group having up to 4 carbon atoms, Y represents an aliphatic arylaliphatic, aromatic or heterocyclic radical, D represents the residue of a coupling compound of the benzene, diphenylene oxide, indazole, coumarin, acetylacetarylide, pyrazolone, or hydroxyquinoline series, D represents the residue of a coupling compound of the benzene, diphenylene oxide, indazole, coumarin, acetylacetarylide, hydroxyquinoline, 1-phenyl-3-methylpyrazolone or l-phenyl-B-carbonamido-pyrazolone series, the nuclei A, B, D D and Y containing no solubilising acid groups.

The residue Y can be, for example a methyl, ethyl, isopropyl, trifluoromethyl, acetylethyl, benzyl, 2,4-dichlorophenoxyethyl, styryl, phenyl, chlorophenyl, toluyl, methoxyphenyl, ,B-furylvinyl or pyridinyl group.

The residues D and D can be substituted, for example, by halogen atoms, alkyl, alkoxy, trifluoromethyl, alkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, hydroxy, acylamino, N-alkylacylamino, aminocarbonyl, aminosulphonyl, alkylaminocarbonyl, alkylaminosulphonyl groups.

The dyestuffs of formulae Ia and 1b in which m represents zero may be prepared, for example by diazotising a base of the general formula:

diazotising the amino-monoazo dyestuff thus obtained and coupling with a coupling compound D H or D H.

The dyestuffs of formula (I) may also be prepared by acylating dyestuffs of the formula:

III

by means of an acid chloride Y--COC1 in the presence of an acid-absorbing agent, possibly in an inert diluent, or by means of an acid anhydride (Y-CO) 0. This method can only be carried out, however, if the dyestuif of formula (III) does not contain any other acylatable group than the OH group carried by the radical X.

The bases of formula (-11) may themselves be prepared, for example, by the following processes:

(1) Starting from a benzoylnitrochloride by condensation with an acylglycol of formula Y-COO-X-OH and reduction of the nitro group. or by condensation with a glycol, acylation by means of an acid chloride YCOC1 or an acid anhydride (YCO) O and reduction of the nitro group, or (2) Starting from a nitrobenzoic acid by esterification by means of an acylglycol Y-COO--XOH and reduction of the nitro group.

by esterification by means of a glycol, acylation as before and reduction of the nitro group or by oxyalkylation, acylation as before and reduction of the nitro group, or

(3) By trans-esterification of a methyl or ethyl nitrobenzoate with a glycol or an acylglycol possible acylation as before, and reduction of the nitro group, or

(4) By trans-esterification of a methyl or ethyl aminobenzoate with an acylglycol YCOOXOH or (5) By esterification of an aminobenzoic acid with an acylglycol YCOO-XOH.

In view of their tinctorial applications, it is advantageous for the dyestuffs obtained to be in a finely divided state. This is why the dyestuffs according to the present invention are preferably previously dispersed and provided in the form of a paste or powder. This form may be realised by mixing the dyestuffs in the form of a paste with dispersing agents, and possibly with inert diluents. This mixing may be followed, if desired, by drying and grinding. The dyestuffs thus treated can then be used for dyeing in a long or short bath, for foularding or printing.

Among the dispersing agents which may be used are for example, the products from the condensation of naphthalenesulphonic acids with formaldehyde, especially dinaphthylmethane-disulphonates, esters of sulphonated succinic acid, alkali metal salts of the sulphuric esters of fatty alcohols, for example sodium lauryl sulphate, lignosulphonates, soaps, alkali metal salts of the sulphuric esters of monoglycerides of fatty acids, the products obtained by condensation of the cresols with formaldehyde and naphtholsulphonic acids, the condensation products of 4,4-dihydroxy-diphenylsulphone with formaldehyde and alkali metal bisulphites.

The dyeing of polyester fibres can be carried out in the presence of a carrier at temperatures ranging from 80 C. to 125 C. or without a carrier under pressure of between 100 C. and about 140 C.

They can also be foularded or printed with an aqueous dispersion of the new dyestuffs, and the impregnation obtained fixed at between 140 C. and 230 C., for example by means of steam, air or by contact with a heated surface. The range of temperature between 180 C. and 200 C. is particularly favourable since the dyestuffs diffuse rapidly into the polyester fibres and do not sublime even if the action of these high temperatures is prolonged. This enables clogging or fouling of the dyeing apparatus to be avoided.

Cellulose diacetate is preferably dyed by exhaustion at between 65 C. and 85 C. and cellulose triacetate and the polyamide fibres are preferably dyed at temperatures up to 115 C. The most favourable range of pH is between 2 and 9 and especially between 4 and 8. The triacetate and the polyamide fibres can be foularded or printed, like the polyester fibres, with an aqueous suspension of the new dyestuffs and the impregnations obtained fixed at between 140 C. and 210 C.

In foularding or printing, the usual thickeners may be used, for example, modified or non-modified natural products such as the alginates, crystalline gum, carob, gum tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products such as poly acrylic amides or polyvinyl alcohols.

The shades thus obtained are remarkably fast to thermal fixation, sublimation, creasing, combustion gases, overdyeing, dry cleaning, chlorine and wet tests, for example,

water, washing and sweat. The reserve of the natural fibres, especially of wool and cotton, and the dischargability are good. The fastness to light is remarkable even with light shades, so that the new dyestuffs are very suit able for the production of fashion shades. The dyestuffs resist boiling and reduction at temperatures between C. and 220 C. This stability is not altered by the bath ratio nor by the presence of dyeing accelerators.

The new dyestuffs can also be used for dyeing polyolefine fibres, fibres based on polymers or copolymers of acrylonitrile or based on polyvinyl derivatives.

Certain dyestuffs of formula (I) lend themselves to the colouration in bulk of varnishes, oils, synthetic resins and synthetic fibres spun from their solutions in organic solvents. Some of these dyestuffs are also remarkably adapted to the dyeing of synthetic fibres modified by a metal, for example, nickel polyolefine fibres.

The invention is illustrated by but not limited to the following examples in which the parts are parts by weight unless the contrary is indicated.

EXAMPLE 1 205.1 parts of the potassium salt of para-nitrobenzoic acid are mixed with parts of glycol chlorhydrin and the mixture is heated under reflux until condensation is complete. 196 parts of ethylene glycol p-nitrobenzoate (mp. 7676.5 C.) are obtained which is heated under reflux in 112 parts of acetic anhydride. When the reaction is finished, the fl-acetyloxyethyl ester of the p-nitrobenzoic acid is isolated in a mixture of water and ice. It melts at 71 C. (73 C. after recrystallisation from a mixture of water and alcohol).

ANALYSIS 0 II N Percent:

Calculated 52. 17 4. 34 5. 53 Found 52. 92 4. 67 5. 58

By reduction of this ester, for example by the Bchamp method, the O-acetyloxyethyl ester of p-aminobenzoic acid is obtained which melts at 94 C. When recrystallized from a mixture of water and methyl alcohol, this product melts at 9697 C.

ANALYSIS 0 II N Percent:

Calculated" 59. 10 5. 83 6. 28 59. 13 6. 19 6. 29

EXAMPLE 2 ANALYSIS Percent:

Calculated 69. 23 5. 76 4. 48 Found 69. 13 5 44 4.00

Prepared in an identical way, the fl-benzoyloxyethyl ester of p-aminobenzoic acid melts at 134-135 C.

ANALYSIS Percent:

Calculated 67. 36 5. 27 4. 91 Found 67. 1O 5. 88 5. 07

EXAMPLE 3 TABLE AContinued 50 parts of [4 B hydroxyethoXycarbonyl-benzene]- Example Shade on 1 azo 4 -[1 phenyl 3 methyl-S-hydroxy-pyrazole] No. Coupling compound DM or DZH polyester are heated 2 hours under reflux. Wltt} 200 Parts of 18 N-r nethyl-N-eyanoethyl-metatoluidine. Yellow orange. acetic anhydnde. A part of the acetic acid formed and a? i-g g l i -gp y e a the excess anhydride is driven oif and the product is left ggi g mnnamoylammo' to crystallise and the crystals are filtered oif. The cryshyly y y a Reddish y wtalhsation can be accelerated by adding alcohol or petrol 2 Yellow ether. The paste of dyestuif obtained is then mixed with g fiathyl-N-hydmxyethyl-aniline Orangea dispersing agent, for example a cresol-formaldehyde- 4 Elli? Yellow naphtholsulphonic acid condensation product and used llgT-cyanoetflyl-tetrahydroqvinoline 5 .ara-ereso 0- as such aflier y 27--. Ethyl cyanaeetate Do.

When applied on polyester fibres, for example by means 2 511 h h-tin Y y roxy- -s p onami o-nap a one... e ow orange. of a dyebath atabout 100 C. with the addition of a 30 2mmn0 6 methylammosulphenyp Orangg carrier, or at high temperature between 120 C. and 31 gfgf g In oxid B Oran 6 1:0 C. 103 by printing, foul-ailing ling tl llermal fix g 11f: i i mii-caibaziif.-. "I j ii g e acety erivative gives aye ow s a e aving exce ent Y e 34.-. 1-hydroxy-4-sulphenam1 o-naphthalene Yellow brown. faStneSS t0 and sublimation. gg g-gygr y-%Ic?l onai i l' jdo-n%phfli1;,lsene gefll orange.

y roxy- -me oxy-p ieny e 0w. carbonamido-naphthalene EXAMPLE 4 q 1 Yellow orange. 111.5 parts of the fl-acetyloxyethyl ester of p-amino- 8-hydroxyumo11nc Brown on nickel 1 1 benzoic acid are dissolved in 1000 parts of water and 110 p0 ypmpy em parts 'by volume of hydrochloric acid and are diazo- On operating as in Example 4 from diazotisable bases tised by adding parts of sodium nitrite. The solution and coupling compounds indicated in Table B below, of the diazo derivative is introduced into a solution of 105 25 other monoazo dyestufis are obtained of which the shades parts of 1-phenyl-3-carbon-amido-S-pyrazolone in 2000 on polyester fibres are indicated in the last column.

TABLE B Example Shade on No. Diazotisable base Coupling compound D1H or DzH polyester fl-Cinnamoyloxyethyl ester of p-aminobenzoic acid 1-phenyl-3-methyl-5-pyrazolone -(Phenylecety1oxy)ethyl ester of p-aminobenzoic acid 0 fl-K a4'-diehloro-phenoxy)acetyloxylethyl ester of p'aminobenzoic IIdo aci B-Benzoyloxyethyl ester of p-aminobenzoic acid..- do Do. B-Acryloyloxyethyl ester of p-aminobenzoic acid fl-Acetyloxyethyl ester of m-arninobenzoic acid ..d0 'y-Acetyloxypropyl ester of p-aminobenzoie acid- 4g fl-Acgyloxyethyl ester of anthranilic acid 28.- do l-phenyl-(i-earbonamido-5-pyrazolone Do.

parts of water containing 120 parts of sodium carbonate EXAMPLE 49 and 200 parts of sodium acetate. The dyestuff obtained is isolated in the conventional manner, mixed with a dis- 111.5 Parts Of the fly yy st r Of p-aminopersing agent and if desired dried, It dye polyester fibr benzoic acid are diazotised as in Example 4 and the solua yellow shade possessing excellent general fastness, partion of the diazo derivative is introduced into a solution ticularly to light and sublimation. of 61.5 parts of m-anisidine dissolved in 100 parts of 30% On replacing the 1-phenyl-3-carbonamide 5 hydrochloric acid and 1000 parts of water. The coupling azolone in Example 4 by the coupling compounds enuis diazotised by means of 35 parts of sodium nitrite. merated in the following Table A oth ono dyethe mixture is filtered and the precipitate obtained is made stuifs are obtained of which the shade on polyester fibres i to a paste in 5000 parts of water, 200 parts of 30% is indicated in the third column. hydrochloric acid are added and the amino-azo compound in diazotised by means of 35 parts of sodium nitrite. TABLEA The solution of the diazo derivative is introduced into Example Shade on 87 parts of l-phenyl-3-methyl-5-pyrazolone dissolved in Coupling mmpmmd DIH D111 Polyester 2000 parts of water by means of 20 parts of caustic soda 5 l-pheny1-3-methyl-5-pyraz01one Yellow, and 0 Pa s of s f C bQ t The dyestuflf obtained 6 gggf g' Greemsh Yellowis isolated by filtration and mixed with a dispersing agent 7 3-r gt zi iyl-5-pyrazolone Do. and dried if desired. It dyes polyester or triacetate fibres 8 'ggiggggfi Yenw' a reddish orange shade possessing excellent general fast- 9-- 3-nitro-1-phenyl-3-methyl-5-pyrazolone Do. ness, especially to light and sublimation. ii I lj iigfigffiifi'fifil fififili25 2; Table C below groups together other examples of disazo ggggg fg Graemhyeuow' dyestuffs p p as 111 E p 49 y dlazotlsmg t 13 N-hydroxyethyl4-hydroxy-2-quinolone...- Do. B-acetyloxyethyl ester of p-annnobenzoic acid, coupling i:::::::: filfifi y ifiifiififi tigi fififii f::::::-.:: eediiil yellow. wi h an mino coupling compound H:B-NH diazotising 1e Ethyl ester of N-ethyl-N -(3-methyl- Yellow orange. the monoazo dyestuq and coupling with a coupling D H 17 NpNhelgliglzgammopropromc ae1d. or D H- yanoethyl) metato1u1d1ne... Yellow. 2

TABLE Example number 1st coupling compound HB-NH: Final coupling compound D H or DzH Shade on polyester 1-phenyl-3-ethoxycarbonyl-5-pyrazolone. Scarlet. l-phenyl-S-earbonamido--pyrazolone.. D0. l-phenyl-iiethoxycarbonyl-fi-pyrazolone Orange. 1- henyl-3-carbonamido-5-pyrazolone. Red orange. 2- ydroxy-3-carbonamidctoluene Orange. 1-phenyl-3-methyl-5pyrazolone. Do.

henol Yellow orange. 2-hydroxy-3-carbonamido naphthalen Bluish red. 1-hydroxy-3carbonamido toluene. Yellow. N methyl-4-hydroxy-2-quinolone Orange. Phen D0 1-phenyl3 methyl 5 pyrazolone Red. do hen Scarlet. a-Naphthylamine. o-Cresol Brown orange.

d l-phenyl-3-m ethyl 0.

a-Naphthol Violet. d 2-hydroxy-3-carbonamldo-toluene Orange N-acetyl-m-phenylenediamine 1-phenyl-3-carbonamido-fi-pyrazolone Scarlet.

EXAMPLE 68 period of half an hour and dyeing is continued at the boil for an hour. After finishing treatment, a yellow shade of excellent fastness to light and sublimation is obtained.

We claim: 1. A compound of the formula:

An ethylene glycol polyterephthalate fabric is impregnated by foularding with a bath which contains per 1000 parts, 9.0 parts of the dyestuff obtained in Example 14, 0.5 part of a polyglycol ether or oleyl alcohol, 1.5 parts of a polyacrylic amide and the quantity of water necessary to make up to 1000 parts. After drying, the fabric is subjected to thermal fixation for 1 minute at 200 C. and then to a reducing treatment with sodium dithionite. A greenish yellow shade having good fastness to light and sublimation is obtained.

CO0-X-O-COY wherein X represents an alkylene radical having up to 4 carbon atoms and Y is methyl, ethyl, isopropyl, trifiuoromethyl, acetylethyl, benzyl, 2',4-dichlorophenoxy-methyl,

EXAMPLE 69 2',4'-diehlorophenoxyethyl, vinyl, styryl, phenyl, chloro- An ethylene glycol polyterephthalate fabric is printed P y y YP Y with a printing paste which contains, per 1000 parts, 20 The compound of Clalm 1 wherein X 15 ethyleneparts of the dyestuff described in Example 51, 150 parts A compound of the formula! of the sodium salt of a sulphonated castor oil, 600 parts of a thickener and 250 parts of Water. After drying, the CHrCO- i a'OCONHg fabric is subjected to thermal fixation for one minute at 200 C., and then to a reducing treatment. A scarlet shade References Cit d having good fastness to light and sublimation is obtained. UNITED STATES PATENTS EXAMPLE 70 40 3,271,440 9/1966 Thomas 260-471 R 100 parts of a cellulose triacetate fabric is introduced at 70 C. in a dycbath of 3000 parts which contains LORRAINE WEINBERGER Primary Examiner 1 part of the dyestuif described in Example 4 and 15 parts of o-phenyl-phenol. The bath is brought to the boil in a THAXTON Asslstant Exammer 

1. A COMPOUND OF THE FORMULA: 